Polymer modified polyphenol compositions and thermosettable resins thereof

ABSTRACT

A composition comprising (A) a polyphenol such as bisphenol A, (B) a polymer resulting from polymerizing (1) an alkenyl phenol such as p-isopropenylphenol and (2) a polymerizable ethylenically unsaturated monomer such as 2-ethylhexyl acrylate can be converted to a copolymer modified polycyanate by reaction with a cyanogen halide such as cyanogen chloride in the presence of a base such as triethylamine. These polycyanates can be cured by trimerization in the presence of a suitable catalyst or by copolymerization with an epoxy resin. Epoxy resins can also be prepared from the composition comprising components (A) and (B) by reaction with an epihalohydrin such as epichlorohydrin and subsequent dehydrohalogenation with a basic acting compound such as a sodium hydroxide.

CROSS-REFERENCE TO RELATED APPLICATION

This is a divisional, of application Ser. No. 747,632, filed June 24,1985.

BACKGROUND OF THE INVENTION

The present invention provides novel compositions consisting of apolyphenol containing a copolymer of an ethylenically unsaturatedcompound and an alkenylphenol, as well as epoxy resins, advanced epoxyresins and polycyanates thereof.

Preparation of polymer modified cyanate and/or cyanamide compositions isdisclosed by Robert E. Hefner, Jr. in application Ser. No. 710,210 filedMar. 11, 1985, now U.S. Pat. No. 4,559,399. In the process, thecopolymer of an alkenylphenyl cyanate and an ethylenically unsaturatedcompound in an aromatic polycyanate or polycyanamide is prepared. Saidproduct is cured by cyclotrimerization to provide a polymer modifiedpolytriazine or by copolymerization with an epoxy resin.

Preparation of polymer modified cyanate mixture compositions consistingof a mixed cyanate of a polyphenol containing a copolymer of anethylenically unsaturated compound and an alkenylphenyl cyanate, as wellas hydroxyaromatic oligomers, epoxy resins and advanced epoxy resinsthereof is taught by Robert E. Hefner, Jr. in application Ser. No.691,801 filed Jan. 15, 1985, now U.S. Pat. No. 4,546,131.

Although each of the aforementioned inventions provided thermosettableresin compositions which, when cured, possess excellent overall physicaland mechanical properties, the present invention provides a prccess tomake polymer modified cyanate compositions without the need for apreformed alkenylphenyl cyanate component. Furthermore, novel polymermodified epoxy resins and advanced epoxy resins with excellent overallphysical and mechanical properties are provided by the presentinvention.

SUMMARY OF THE INVENTION

One aspect of the present invention concerns a composition whichcomprises

(A) a polyphenol represented by the formulas ##STR1## wherein each A isindependently a divalent hydrocarbon group having from 1 to about 12,preferably from 1 to about 6 carhon atoms, --S--, --S--S--, ##STR2## or--O--; each A' is a divalent hydrocarbon group having from 1 to about 3,preferably 1, carbon atoms or a ##STR3## each R' is independentlyhydrogen, an aliphatic or aromatic hydrocarbyl or hydrocarbyloxy grouphaving from 1 to about 10 carbon atoms, chlorine or bromine; p has avalue of from zero to about 10, preferably from zero to 3; n has a valueof zero or 1 and n' has a value from about 0.001 to about 6; and

(B) a polymer resulting from copolymerizing

(1) an alkenylphenol or a mixture of alkenylphenols represented by theformula ##STR4## wherein Z is a ##STR5## each R, R¹ and R² isindependently hydrogen or a hydrocarbyl group having from 1 to about 3carbon atoms; each R' is independently hydrogen, an aliphatic oraromatic hydrocarbyl or hydrocarbyloxy group having from 1 to about 10carbon atoms, chlorine or bromine; x has a value of 4; and

(2) a polymerizable ethylenically unsaturated monomer or mixture of suchmonomers; wherein component (A) is present in quantities of from about10 to about 99, preferably from about 50 to about 95, most preferablyfrom about 75 to about 90 percent by weight (% bw); component (B-1) ispresent in quantities of from about 0.1 to about 50, preferably fromabout 0.5 to about 10, most preferably from about 1 to about 5% bw;component (B-2) is present in a quantity of from about 1 to about 50,preferably from about 5 to about 25, most preferably from about 10 toabout 20% bw and wherein the amount of the individual components isbased upon the combined weight of components (A) and (B).

Another aspect of the present invention pertains to a process forpreparation of polymer modified cyanate compositions. In the process,the copolymer of an alkenylphenol and an ethylenically unsaturatedcompound in an aromatic polyphenol is prepared. Said product is thenreacted with stoichiometric or a slight stoichiometric excess (up toabout 20 percent by weight excess) of a cyanogen halide in the presenceof a suitable base, such as triethylamine. This provides a copolymer ofan alkenylphenyl cyanate and ethylenically unsaturated compound in anaromatic polycyanate. Said product may be cured by cyclotrimerization orby copolymerization with an epoxy resin.

Another aspect of the present invention pertains to polymer modifiedpolyepoxide compositions. Said compositions are prepared by epoxidizingthe copolymer of an alkenylphenol and an ethylenically unsaturatedcompound in an aromatic polyphenol in a conventional manner by reactingwith an epihalohydrin with subsequent dehydrohalogenation with abasic-acting material. This provides a copolymer of an alkenylphenylglycidyl ether and ethylenically unsaturated compound in a polyglycidylether of a polyphenol.

Another aspect of the present invention pertains to advanced epoxy resincompositions containing the copolymerization product of an alkenylphenoland an ethylenically unsaturated compound. Said compositions areprepared by reacting a polyphenol containing the copolymerizationproduct of an alkenylphenol and an ethylenically unsaturated compoundwith an epoxy resin or mixture of epoxy resins wherein about 0.01 to0.99 mole, preferably 0.1 to 0.6 mole of hydroxy groups per mole ofepoxide groups are provided.

An additional aspect of the present invention pertains to the productresulting from curing a composition comprising the aforementionedpolymer modified epoxy resins or advanced epoxy resins and a curingquantity of a catalyst and/or curing agent therefor.

DETAILED DESCRIPTION OF THE INVENTION

Particularly suitable alkenylphenols which can be employed hereininclude, for example, p-isopropenyl phenol, p-vinylphenol,m-vinylphenol, methyl-p-isopropenyl phenol, 3-chloro-4-isopropenylphenol, p-allylphenol, p-methallylphenol, m-allylphenol, o-allylphenol,2,6-dimethyl-4-allylphenol, mixtures thereof and the like. It is mostpreferred that the alkenylphenol be substantially free of dimeric and/oroligomeric components although it is operable to use an alkenylphenolcontaining substantial (up to 90% bw) dimeric and/or oligomericcomponents.

The polyphenols employed herein which are represented by formulas I, II,III, IV include, for example, bisphenol A (4,4'-isopropylidenediphenol), resorcinol, hydroquinone, 4,4'-dihydroxydiphenyl oxide,4,4'-thiodiphenol, 4,4'-sulfonyldiphenol, 3,3', 5,5'-tetrabromobisphenolA, 2,2'-dihydroxybiphenyl, 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl, 2,2',6,6'-tetrabromobisphenolA, 2,2',6,6'-tetramethyl-3,3',5,5'-tetrabromobisphenol A,3,3'-dimethoxybisphenol A, the bisphenol of dicyclopentadiene, thebisphenol of tricyclopentadiene, ##STR6## phenolformaldehydecondensation products (novolac), phenol-dicyclopentadiene condensationproducts, 2,2',4,4'-tetrahydroxydiphenyl methane,tris(hydroxyphenyl)methane, mixtures thereof and the like.

Suitable ethylenically unsaturated monomers which can be employed hereininclude any of the known monomers which are polymerizable. Mostpreferred as the ethylenically unsaturated monomer are the acrylate ormethacrylate esters represented by the formula ##STR7## wherein R³ is ahydrocarbyl group having from 2 to about 25 carbon atoms and may bebranched, cyclic, or polycyclic and R⁴ is hydrogen or a methyl group.

Typical acrylate esters represented by formula VI include ethylacrylate, n-butyl acrylate, n-butyl methacrylate, sec-butyl acrylate,2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-dodecyl acrylate,cyclohexyl acrylate, methyl cyclohexyl acrylate, norbornyl acrylate,dicyclopentadiene acrylate, methyl dicyclopentadiene acrylate, mixturesthereof and the like.

Equally preferred as the ethylenically unsaturated monomer are the vinylaromatic compounds represented by the formula ##STR8## wherein R' and R⁴are as hereinbefore defined.

Typical vinyl aromatic compounds represented by formula VII includestyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene,α-methylstyrene, chlorostyrene, bromostyrene, t-butylstyrene,phenylstyrene, p-methoxystyrene, t-butyl-α-methylstyrene, mixturesthereof and the like.

Although less preferred, any other of the known polymerizableethylenically unsaturated compounds can be employed herein either aloneor in any combination. Typical of these compounds are butadiene,isoprene, allylbenzene, diallylbenzene, diallylphthalate, acrylonitrile,vinyl chloride, vinyl bromide, vinyl acetate, vinyl naphthalene, thepoly(ethoxy)acrylate of dicyclopentadiene, mixtures thereof and thelike.

In a most preferred process of the present invention, an alkenylphenoland an ethylenically unsaturated monomer are copolymerized in thepresence of 0.01 to 5 percent of a suitable free radical formingcatalyst and at a suitable reaction temperature while in solution oradmixture with the polyphenol. Operable free radical forming catalystsinclude but are not limited to the organic peroxides or hydroperoxides,persulfates, and azo or diazo compounds. Most preferred free radicalforming catalysts are t-butyl peroxybenzoate, azobisisobutyronitrile,dicumylperoxide and di-t-butylperoxide. Suitable reaction temperaturesare from about 70° C. to about 190° C. The alkenylphenol andethylenically unsaturated monomer may first be mixed to form a solutionwhich is added to the polyphenol. Alternately, the ethylenicallyunsaturated monomer may be added to a solution or admixture of thealkenylphenol and polyphenol. The product resulting from thiscopolymerization is an ethylenically unsaturated monomer andalkenylphenol copolymer dissolved in or mixed with a polyphenol.Depending on the amounts and types of alkenylphenol and ethylenicallyunsaturated monomer used, significant amounts of homopolymer of theethylenically unsaturated compound and/or alkenylphenol may also bepresent. Significant amounts of unreacted ethylenically unsaturatedmonomer and/or alkenylphenol may also be present. Reduction of saidunreacted ethylenically unsaturated monomer and/or alkenylphenol in thefinal product may be accomplished by vacuum distillation or stripping toinduce partial or total removal or by post-treatment of the reactionproduct with additional free radical forming catalyst to induce furtherpolymerization. It is to be understood that the term copolymerencompasses not only polymers but also oligomers and dimers.

In an alternate, although less preferred, process of the invention, analkenylphenol and ethylenically unsaturated monomer are copolymerizedthen the resulting ethylenically unsaturated monomer and alkenylphenolcopolymer is then added to the polyphenol.

An inert solvent may be used in any of the aforementioned processes ofthe present invention. Said solvent can be used for many known purposes:dissolution or suspension of the polyphenol, modification ofpolymerization kinetics, manipulation of copolymer average molecularweight and the like. In a preferred process of the present invention,the alkenylphenol and ethylenically unsaturated monomer arecopolymerized in a suspension (mixture) of a polyphenol in a solvent inwhich it is substantially insoluble. The solvent is removed by vacuumdistillation or stripping prior to use of the product.

The product ethylenically unsaturated monomer and alkenylphenolcopolymer in a polyphenol may be used to prepare a copolymer of analkenylphenyl cyanate and ethylenically unsaturated compound in anaromatic polycyanate as is hereinbefore described.

The product ethylenically unsaturated monomer and alkenylphenolcopolymer in a polyphenol may be used to prepare a copolymer of analkenylphenyl glycidyl ether and ethylenically unsaturated monomer in apolyglycidyl ether of a polyphenol. Said compositions can be prepared byreaction of the phenolic hydroxyl groups of the copolymer of anethylenically unsaturated monomer and an alkenylphenol in a polyphenolwith an epihalohydrin and a basic acting material. Said reactiongenerally involves two distinct steps: coupling reaction of theepihalohydrin and phenolic hydroxyl groups and dehydrohalogenationreaction of the halohydrin intermediate to provide the glycidyl etherproduct. Suitable catalysts and reaction conditions for preparingpolyepoxides are described in the Handbook of Epoxy Resins by Lee andNeville, McGraw-Hill (1967) which is incorporated herein by reference.

The product ethylenically unsaturated monomer and alkenylphenolcopolymer in a polyphenol may be used to prepare advanced epoxy resincompositions containing the aforesaid copolymer. Suitable epoxy resinsfor the advancement reaction are represented by the formulas ##STR9##wherein each A, A', R', n, n' are as hereinbefore defined, each R" isindependently hydrogen or an alkyl group having 1 to about 4 carbonatoms and m has a value from zero to about 40, preferably from 0.1 toabout 5.

Particularly suitable polyepoxides which can be employed herein include,for example, the diglycidyl ethers of resorcinol, bisphenol A,3,3',5,5'-tetrabromobisphenol A, the triglycidyl ether oftris(hydroxyphenyl)methane, the polyglycidyl ether of aphenol-formaldehyde condensation product (novolac), the polyglycidylether of a dicyclopentadiene and phenol condensation product and thelike. The polyepoxides can be used either alone or in combination.Suitable catalysts and reaction conditions for preparing polyepoxidesare described in the Handbook of Epoxy Resins by Lee and Neville,McGraw-Hill (1967) which is incorporated herein by reference.

The advancement reaction is optionally, although preferably, performedin the presence of 0.01 to 2 percent by weight of a suitable catalyst.Suitable catalysts include bases, basic acting materials, acids and thelike.

Preferred catalysts are the quaternary ammonium salts and phosphoniumsalts. Most preferred catalysts are ethyltriphenylphosphonium halidesand benzyltrimethyl ammonium halides. Reaction temperatures and timesvary depending on the composition of the epoxy resin reactant used; theamount and type of catalyst used, if any; the presence of inert solvent,if any. Typically, the advancement reaction when catalyzed is conductedat a temperature of from about 50° C. to about 200° C., preferably fromabout 90° C. to about 150° C. for from about 15 minutes (900 s) to about240 minutes (14,400 s), preferably from about 30 minutes (1800 s) toabout 90 minutes (5400 s). Advancement reaction times and temperaturesare generally longer and higher, respectively, for the non-catalyzedreaction.

Suitable curing agents and/or catalysts for curing and/or preparingepoxy resins and advanced epoxy resins are described in the Handbook ofEpoxy Resins by Lee and Neville, McGraw-Hill (1967), as well as U.S.Pat. Nos. 3,477,990; 3,948,855 and 4,366,295 which are incorporatedherein by reference.

The cured epoxy resins and advanced epoxy resins of this inventionpossess improvements in one or more physical or mechanical properties,such as tensile strength and percent elongation. Furthermore, theadvancement reaction allows for incorporation of the polyphenolcontaining the copolymerization product of an alkenylphenol and anethylenically unsaturated compound without having to epoxide (i.e.,react with an epihalohydrin followed by dehydrohalogenation) saidpolymer modified polyphenol.

The epoxy resins and advanced epoxy resins of the present invention canbe used to prepare castings, coatings, laminates, composites,encapsulations and the like, and are especially suited for use inapplications requiring high mechanical strength. If desired, solvent,fillers, pigments, flow control agents, dyes, fire suppressants andother additives can be employed.

The following examples are illustrative of the invention, but are not tobe construed as to limiting the scope thereof in any manner.

EXAMPLE 1 A. Copolymerization of 2-Ethylhexyl Acrylate andp-Isopropenylphenol in a Bisphenol A Solution

A 228.3 gram (75 percent by weight, % bw) portion of bisphenol A wasadded to a reactor maintained under a nitrogen atmosphere. The reactorcontents were heated to a 150° C. solution then stirring commenced and amixture of 2-ethylhexylacrylate (66.88 grams, 22 % bw),p-isopropenylphenol (9.12 grams, 3% bw) and t-butylperoxybenzoate (2.28grams, 3% bw based on a 2-ethylhexylacrylate and p-isopropenylphenolused) were added dropwise over a 75 minute (4500 s) period. After anadditional 60 minutes (3600 s) of reaction at the 150° C. reactiontemperature, the product was recovered as a crystalline, light yellowcolored solid at room temperature (25° C.). Gel permeationchromatographic analysis of a portion of the product demonstratedessentially quantitative conversion of the 2-ethylhexylacrylate andp-isopropenylphenol to cooligomer dispersed in unchanged bisphenol A.

B. Cyanation of Copoly(2-Ethylhexylacrylate and p-Isopropenylphenol) inBisphenol A

A 295 gram (2.004 moles of hydroxyl groups) portion ofcopoly(2-ethylhexylacrylate and p-isopropenylphenol) in bisphenol A fromA above, 222.92 grams (2.104 moles) of cyanogen bromide and 1500milliliters of acetone were added to a reactor and maintained under anitrogen atmosphere with stirring. The stirred solution was cooled to-5° C. then 203.82 grams (2.014 moles) of triethylamine were added tothe reactor over a twenty minute (1200 s) period so as to maintain thereaction temperature at -5° C. to -3° C. After completion of thetriethylamine addition, the reactor was maintained at -5° C. to -3° C.for an additional forty-five minutes (2700 s) followed by addition ofthe reactor contents to 1.5 gallons (5.685 l) of deionized water. After5 minutes (300 s), the water and product mixture was extracted with two500 milliliter portions of methylene chloride. The combined methylenechloride extract was washed with 500 milliliters of 1 percent aqueoushydrochloric acid followed by washing with 1000 milliliters of deionizedwater then drying over anhydrous sodium sulfate. The dry methylenechloride solution was filtered and solvent removed by rotary evaporationunder vacuum and at 100° C. for 30 minutes (1800 s). Thecopoly(2-ethylhexylacrylate and p-isopropenylphenyl cyanate) inbisphenol A dicyanate was recovered as a transparent, light ambercolored solution which crystallized to a light tan colored product uponstanding at room temperature (25° C.). Infrared spectrophotometricanalysis of a film sample of the product confirmed the product structure(disappearance of phenolic hydroxyl absorbance, appearance of--O--C.tbd.N absorbance.

COMPARATIVE EXPERIMENT A Preparation of Bisphenol A Dicyanate

A 342.45 gram (1.5 moles) portion of bisphenol A, 333.68 grams (3.15moles) of cyanogen bromide and 1000 milliliters of acetone were added toa reactor and maintained under a nitrogen atmosphere with stirring. Thestirred solution was cooled to -5° C. then 305.09 grams (3.015 moles) oftriethylamine was added to the reactor over a twenty-five minute (1500s) period and so as to maintain the reaction temperature at -5° C. to 0°C. After completion of the triethylamine addition, the reactor wasmaintained at -2° C. to 5° C. for an additional 50 minutes (3000 s),followed by addition of the reactor contents to 1 gallon (3.79) ofchilled deionized water. After 5 minutes (300 s) the water and productmixture was extracted with three 500 milliliter portions of methylenechloride. The combined methylene chloride extract was washed with 500milliliters of 5 percent aqueous hydrochloric acid followed by washingwith 800 milliliters of deionized water then drying over anhydroussodium sulfate. The dry methylene chloride solution was filtered andsolvent removed by rotary evaporation under vacuum. Bisphenol Adicyanate (360.7 grams) was recovered in 86.4 percent yield as a whitecrystalline solid. Infrared spectrophotometric analysis of a film sampleof the product confirmed the product structure (disappearance ofphenolic hydroxyl absorbance, appearance of --O--C.tbd.N absorbance).

EXAMPLE 2 Polymerization of Copoly(2-Ethylhexylacrylate andp-Isopropenylphenyl Cyanate, in Bisphenol A Dicyanate

A 250 gram portion of copoly(2-ethylhexylacrylate andp-isopropenylphenyl cyanate) in bisphenol A dicyanate from Example 1-Bwas heated to 60° C. and 0.25 gram of cobalt naphthenate (6 percentactive) was added. This solution was poured into a 1/8 inch (3.175 mm)mold made from a pair of glass plates and then placed in an oven andmaintained at 125° C. for 2 hours (7200 s) then 177° C. for 2 hours(7200 s). The light amber colored, slightly hazy, unfilled casting wasdemolded and used to prepare test pieces for tensile and flexuralstrength, flexural modulus, percent elongation and average Barcolhardness (934-1 scale) determinations. Mechanical properties of tensile(6) and flexural (5) test pieces were determined using an Instronmachine with standard test methods (ASTM D-638 and D-790). The resultsare reported in Table I.

COMPARATIVE EXPERIMENT B Polymerization of Bisphenol A Dicyanate

A 161.3 gram portion of bisphenol A dicyanate from ComparativeExperiment A was heated to 60° C. and 0.16 gram of cobalt naphthenate (6percent active) was added. This solution was used to prepare a clear,unfilled 1/8 inch (3.175 mm) casting using the method of Example 2. Themechanical properties of the transparent, light amber colored, unfilledcasting were determined using the method of Example 2. The results arereported in Table I.

                  TABLE I                                                         ______________________________________                                                                Comparative                                                       Example 2   Experiment B                                          ______________________________________                                        Barcol Hardness                                                                             26            48                                                Tensile Strength,                                                                           6292/43,382   7258/50,042                                       psi/kPa                                                                       Elongation (%)                                                                              5.05          1.42                                              Flexural Strength,                                                                          13,329/91,901 11,727/80,855                                     psi/kPa                                                                       Flexural Modulus,                                                                           349,000/2,406,285                                                                           660,000/4,550,568                                 psi/kPa                                                                       ______________________________________                                    

EXAMPLE 3 A. Copolymerization of (2-Ethylhexylacrylate andp-Isopropenylphenol) in a Bisphenol A Solution

A 228.3 gram (80 percent by weight, % bw) portion of bisphenol A wasadded to a reactor maintained under a nitrogen atmosphere. The reactorcontents were heated to a 150° C. solution then stirring commenced and amixture of 2-ethylhexylacrylate (42.81 grams, 15% bw),p-isopropenylphenol (14.27 grams, 5% bw) and t-butylperoxybenzoate (1.14grams, 2% bw based on 2-ethylhexylacrylate and p-isopropenylphenol used)were added dropwise over a 45 minute (2700 s) period. After anadditional 60 minutes (3600 s) of reaction at the 150° C. reactiontemperature, the product was recovered as a crystalline, light yellowcolored solid at room temperature (25° C.). Gel permeationchromatographic analysis of a portion of the product demonstratedessentially quantitative conversion of the 2-ethylhexylacrylate andp-isopropenylphenol to cooligomer dispersed in unchanged bisphenol A.

B. Cyanation of Copoly(2-Ethylhexylacrylate and p-Isopropenylphenol) inBisphenol A

A 285.4 gram (2.1064 moles of hydroxyl groups) portion ofcopoly(2-ethylhexylacrylate and p-isopropenylphenol) in bisphenol A fromA above, 234.79 grams (2.212 moles) of cyanogen bromide and 1200milliliters of acetone were added to a reactor and maintained under anitrogen atmosphere with stirring. The stirred solution was cooled to-7° C. then 214.21 grams (2.106 moles) of triethylamine were added tothe reactor over a twenty-four minute (1440 s) period and so as tomaintain the reaction temperature at -7° to -4° C. After completion ofthe triethylamine addition, the reactor was maintained at -5° to -4° C.for an additional forty-five minutes (2700 s) followed by addition ofthe reactor contents to 1.5 gallons (5.685 l) of deionized water. After5 minutes (300 s), the water and product mixture was extracted with two500 milliliter portions of methylene chloride. The combined methylenechloride extract was washed with 500 milliliters of 1 percent aqueoushydrochloric acid followed by washing with 1000 milliliters of deionizedwater then drying over anhydrous sodium sulfate. The dry methylenechloride solution was filtered and solvent removed by rotary evaporationunder vacuum and at 100° C. for 30 minutes (1800 s). Thecopoly(2-ethylhexylacrylate and p-isopropenylphenyl cyanate) inbisphenol A dicyanate was recovered as a transparent light amber coloredsolution (330.2 grams) which crystallized to a light tan colored productupon standing at room temperature (25° C.). Infrared spectrophotometricanalysis of a film sample of the product confirmed the product structure(disappearance of phenolic hydroxyl absorbance, appearance of--O--C.tbd.N absorbance).

C. Polymerization of Copoly(2-Ethylhexylacrylate and p-IsopropenylphenylCyanate) in Bisphenol A Dicyanate

A 250 gram portion of copoly(2-ethylhexylacrylate andp-isopropenylphenyl cyanate) in bisphenol A dicyanate from B above wasused to prepare a clear, unfilled 1/8 inch (3.175 mm) casting using themethod of Example 2. The mechanical properties of the transparent, lightamber colored, unfilled casting were determined using the method ofExample 2. The results are reported in Table II and may be directlycompared with Comparative Experiment B as reported in Table I.

                  TABLE II                                                        ______________________________________                                        Barcol Hardness      37                                                       Tensile Strength, psi/kPa                                                                          8941/61,646                                              Elongation (%)       3.59                                                     Flexural Strength, psi/kPa                                                                         16,624/114,619                                           Flexural Modulus, psi/kPa                                                                          456,587/3,148,076                                        ______________________________________                                    

EXAMPLE 4 A. Epoxidation of Copoly(2-Ethylhexylacrylate andp-Isopropenylphenol) in Bisphenol A

A 175 gram (1.2265 moles of hydroxyl groups) portion ofcopoly(2-ethylhexylacrylate and p-isopropenylphenol) in bisphenol Aprepared using the method of Example 3-A, 567.42 grams (6.1323 moles) ofepichlorohydrin, 305.53 grams (35 percent by weight, % bw, ofepichlorohydrin used) of isopropanol and 49.34 grams (8% bw ofepichlorohydrin used) of deionized water were added to a reactor andmaintained under a nitrogen atmosphere with stirring. The stirredsolution was heated to 50° C. then 88.3 grams (2.2076 moles) of sodiumhydroxide dissolved in 353.22 grams of deionized water were added to thereactor over a 46 minute (2760 s) period during which time the reactiontemperature was allowed to exotherm and then stabilize at 60° C. Aftercompletion of the aqueous sodium hydroxide addition the reactor wasmaintained at 60° C. for an additional fifteen minutes (900 s) then39.25 grams (1.2265 moles) of sodium hydroxide dissolved in 156.99 gramsof deionized water were added to the reactor, over a twenty-one minute(1260 s) period. After completion of the aqueous sodium hydroxideaddition, the reactor was maintained at 60° C. for an additional fifteenminutes (900 s) then the reactor contents were added to a separatoryfunnel containing 500 grams of deionized water. The organic layer wasrecovered and washed with an additional 500 grams of deionized water.After a third water wash with 1000 grams of deionized water therecovered organic layer was rotary evaporated under vacuum and at 100°C. for 45 minutes (2700 s). The copoly(2-ethylhexylacrylate andp-isopropenylphenyl glycidyl ether) in bisphenol A diglycidyl ether wasrecovered (237.7 grams) as a transparent, light yellow colored liquidwith an epoxide equivalent weight (EEW) of 191.7.

B. Polymerization of Copoly(2-Ethylhexylacrylate and p-IsopropenylphenylGlycidyl Ether) in Diglycidyl Ether of Bisphenol A

A 210 gram portion of copoly(2-ethylhexylacrylate andp-isopropenylphenyl glycidyl ether) in diglycidyl ether of bisphenol Afrom A above was heated to 100° C. and thoroughly mixed with 54.22 gramsof 4,4'-diaminodiphenyl methane which was also heated to 100° C. Thissolution was used to prepare a clear, unfilled 1/8 inch (3.175 mm)casting using the method of Example 2. The mechanical properties of thetransparent, light yellow colored, unfilled casting were determinedusing the method of Example 2. The results are reported in Table III.

                  TABLE III                                                       ______________________________________                                        Barcol Hardness      40                                                       Tensile Strength, psi/kPa                                                                          12,126/83,606                                            Elongation %         6.37                                                     Flexural Strength, psi/kPa                                                                         21,580/148,790                                           Flexural Modulus, psi/kPa                                                                          461,000/3,178,503                                        ______________________________________                                    

EXAMPLE 5 A. Copolymerization of 2-Ethylhexylacrylate andp-Isopropenylphenol in a Bisphenol A and Toluene Mixture

A 45.66 gram (37.84 percent by weight, % bw) portion of bisphenol A andtoluene (65 grams) was added to a reactor and maintained under anitrogen atmosphere as a stirred slurry. The reactor contents wereheated to 90° C. then stirring of the slurry commenced and a solution of2-ethylhexylacrylate (67.5 grams, 55.94% bw), p-isopropenylphenol (7.5grams, 6.22% bw) and azobisisobutyronitrile (0.225 gram, 0.3% bw basedon 2-ethylhexylacrylate and p-isopropenylphenol used) was added dropwiseover a two hour (7200 s) period. After an additional eight hours (28,800s) at the 90° C. reaction temperature, the product was recovered andsolvent plus unreacted monomer removed by rotary evaporation undervacuum at 110° C. for 60 minutes (3600 s). The product (116.9 grams) wasrecovered as a mixture of bisphenol A suspended in a viscous,transparent copolymer of 2-ethylhexylacrylate and p-isopropenylphenol.

B. Advancement of a Diglycidyl Ether of Bisphenol A UsingCopoly(2-Ethylhexylacrylate and p-Isopropenylphenol) in Bisphenol A

A 116.9 gram (0.4 mole of hydroxyl groups) portion ofcopoly(2-ethylhexylacrylate and p-isopropenylphenol) in bisphenol A fromA above and a diglycidyl ether of bisphenol A having an epoxideequivalent weight (EEW) of 181.5 (4.8 moles of epoxide groups, 871.34grams) were added to a reactor and maintained under a nitrogenatmosphere with stirring. The stirred solution was heated to 90° C. then0.87 gram (0.1% bw based on bisphenol A) of tetrabutylphosphoniumacetate.acetic acid complex (70% bw in methanol) was added to thereactor after which time the reaction temperature was increased to 150°C. over a thirteen minute (780 s) period. After 90 minutes (5400 s) ofreaction at the 150° C. reaction temperature, the polymer modifiedadvanced epoxy resin was recovered (987.8 grams) as a opaque, whiteliquid with an epoxide equivalent weight (EEW) of 223.61.

C. Polymerization of Polymer Modified Advanced Epoxy Resin

A 240 gram portion of the polymer modified advanced epoxy resin from Babove was heated to 100° C. and thoroughly mixed with 53.13 grams of4,4'-diaminodiphenyl methane which was also heated to 100° C. Thissolution was used to prepare an unfilled 1/8 inch (3.175 mm) castingusing the method of Example 2. The mechanical properties of the opaque,white unfilled casting were determined using the method of Example 2.The results are reported in Table IV.

                  TABLE IV                                                        ______________________________________                                        Barcol Hardness       31                                                      Tensile Strength, psi/kPa                                                                           10,530/72,602                                           Elongation %          7.1                                                     Flexural Strength, psi/kPa                                                                          17,514/120,755                                          Flexural Modulus, psi/kPa                                                                           426,701/2,942,018                                       Heat Distortion Temperature,                                                                        137/279                                                 °C./°F.                                                         ______________________________________                                    

I claim:
 1. A polymer modified epoxy resin composition which resultsfrom dehydrohalogenating the reaction product of an excess ofepihalohydrin with a composition which comprises(A) a polyphenolrepresented by the formulas ##STR10## wherein each A is independently adivalent hydrocarbon group having from 1 to about 12 carbon atoms,--S--, --S--S--, ##STR11## each A' is a divalent hydrocarbon grouphaving from 1 to about 3 carbon atoms or a ##STR12## each R' isindependently hydrogen, an aliphatic or aromatic hydrocarbyl orhydrocarbyloxy group having from 1 to about 10 carbon atoms, chlorine orbromine; p has a value of from zero to about 10; n has a value of zeroor 1 and n' has a value from about 0.001 to about 6; and (B) a polymerresulting from copolymerizing(1) an alkenylphenol or a mixture ofalkenylphenols represented by the formula ##STR13## wherein Z is a##STR14## each R, R¹ and R² is independently hydrogen or a hydrocarbylgroup having from 1 to about 3 carbon atoms; each R' is independentlyhydrogen, an aliphatic or aromatic hydrocarbyl or hydrocarbyloxy grouphaving from 1 to about 10 carbon atoms, chlorine or bromine; x has avalue of 4; and (2) a polymerizable ethylenically unsaturated monomer ormixture of such monomers; wherein component (A) is present in quantitiesof from about 10 to about 99 percent by weight (% bw); component (B-1)ispresent in quantities of from about 0.1 to about 50% bw; component (B-2)is present in a quantity of from about 1 to about 50% bw and wherein theamount of the individual components is based upon the combined weight ofcomponents (A) and (B).
 2. A polymer modified epoxy resin compositionwherein(i) component (A) is present in quantities of from about 50 toabout 95% bw; (ii) component (B-1) is present in quantities of fromabout 0.5 to about 10% bw; and (iii) component (B-2) is present inquantities of from about 5 to about 25% bw.
 3. A polymer modified epoxyresin composition wherein(i) component (A) is present in quantities offrom about 75 to about 90% bw; (ii) component (B-1) is present inquantities of from about 1 to about 5% bw; and (iii) component (B-2) ispresent in quantities of from about 10 to about 20% bw.
 4. A polymermodified epoxy resin composition wherein(i) component (A) is representedby formula II; (ii) in component (B-1), Z is represented by the formula##STR15## (iii) component (B-2) is an acrylate or methacrylate ester. 5.A polymer modified epoxy resin composition wherein(i) component (A) isbisphenol A; (ii) component (B-1) is p-isopropenylphenol; and (iii)component (B-2) is 2-ethylhexyl acrylate.
 6. The product resulting fromcuring a mixture comprising an epoxy resin of claim 1 with a curingquantity of at least one curing agent or curing catalyst for said epoxyresin.
 7. The product resulting from curing a mixture comprising anepoxy resin of claim 2 with a curing quantity of at least one curingagent or curing catalyst for said epoxy resin.
 8. The product resultingfrom curing a mixture comprising an epoxy resin of claim 3 with a curingquantity of at least one curing agent or curing catalyst for said epoxyresin.
 9. The product resulting from curing a mixture comprising anepoxy resin of claim 4 with a curing quantity of at least one curingagent or curing catalyst for said epoxy resin.
 10. The product resultingfrom curing a mixture comprising an epoxy resin of claim 5 with a curingquantity of at least one curing agent or curing catalyst for said epoxyresin.
 11. The product of claim 6 which is in the form of a coating,casting, composite or laminate.
 12. The product of claim 7 which is inthe form of a coating, casting, composite or laminate.
 13. The productof claim 8 which is in the form of a coating, casting, composite orlaminate.
 14. The product of claim 9 which is in the form of a coating,casting, composite or laminate.
 15. The product of claim 10 which is inthe form of a coating, casting, composite or laminate.